MRI: Acquisition of a SQUID Magnetometer for Analysis of Advanced Materials

Technical Summary: Superconducting quantum interference device (SQUID) magnetometry is a non-destructive technique that reveals detailed information about the electron spin interactions in many types of materials. This project will involve a state-of-the-art SQUID magnetometer and Magnetic Property Measurement System (MPMS), which is a critical tool for characterizing several types of materials currently being investigated by researchers within the Laboratory for Surface Science & Technology (LASST) and other University of Maine (UMaine) laboratories. Specific measurement capabilities include DC and AC magnetic susceptibility, magnetoresistivity, van der Paaw conductivity, and Hall mobility. State-of-the-art MPMS capabilities will be especially valuable to several research programs at UMaine pertaining to (i) surface magnetism in nanoparticles, (ii) magnetic anisotropies in sedimentary rocks, (iii) electrical transport in physical and chemical sensing devices, (iv) optical properties of nanostructures in high magnetic fields, and (v) magnetic nanoparticle based biosensors. The MPMS will serve as a focal point for training undergraduates, graduate students, postdocs, and visiting scientists in magnetic materials, nanotechnology, biophysics, and materials science. This instrument is a critical tool for expanding the capacity of UMaine research into magnetic aspects of nanotechnology, biophysics, sensor technology, and materials science. As no SQUID magnetometer currently exists in the State of Maine, the instrumentation will provide access for research projects from interested parties throughout the state, including non-Ph.D. granting institutions and small Maine businesses. The instrument is relatively easy to operate and provides direct information on electron spin interactions, and thus it will be a powerful tool to teach physics and nanotechnology concepts to several different constituents participating in UMaine outreach activities, including K-12 students and teachers, the general public, under-represented groups, and industry partners.Layman Summary: Superconducting quantum interference device (SQUID) magnetometry is a non-destructive technique that reveals detailed information about the electron spin interactions in many types of materials. Knowledge of electron interactions in materials is extremely important in building the next generation of computers, electronics, and contrast agents in biological magnetic screening techniques (i.e. MRI). To gain the necessary information, a system with control over both the magnetic field strength and temperature is critical. To this end, a SQUID/Magnetic Property Measurement System (MPMS) is ideal for these measurements. This project will purchase a state-of-the-art MPMS system and will be especially valuable to several research programs at UMaine pertaining to surface magnetism in nanoparticles, magnetic anisotropies in sedimentary rocks, electrical transport in physical and chemical sensing devices, and magnetic nanoparticle based biosensors. The proposed MPMS will serve as a focal point for training undergraduates, graduate students, postdocs, and visiting scientists in magnetic materials, nanotechnology, biophysics, and materials science. As no SQUID magnetometer currently exists in the State of Maine, the instrumentation will provide access for research projects from interested parties throughout the state, including non-Ph.D. granting institutions and small Maine businesses. The instrument is relatively easy to operate and provides direct information on electron spin interactions, and thus it will be a powerful tool to teach physics and nanotechnology concepts to several different constituents participating in UMaine outreach activities, including K-12 students and teachers, the general public, under-represented groups, and industry partners

Nature of the positron state in CdSe quantum dots

Previous studies have shown that positron-annihilation spectroscopy is a highly sensitive probe of the electronic structure and surface composition of ligand-capped semiconductor Quantum Dots (QDs) embedded in thin films. Nature of the associated positron state, however, whether the positron is confined inside the QDs or localized at their surfaces, has so far remained unresolved. Our positron-annihilation lifetime spectroscopy (PALS) studies of CdSe QDs reveal the presence of a strong lifetime component in the narrow range of 358-371 ps, indicating abundant trapping and annihilation of positrons at the surfaces of the QDs. Furthermore, our ab-initio calculations of the positron wave function and lifetime employing a recent formulation of the Weighted Density Approximation (WDA) demonstrate the presence of a positron surface state and predict positron lifetimes close to experimental values. Our study thus resolves the longstanding question regarding the nature of the positron state in semiconductor QDs, and opens the way to extract quantitative information on surface composition and ligand-surface interactions of colloidal semiconductor QDs through highly sensitive positron-annihilation techniques.Comment: 14 pages, 3 figure

Eu³⁺-Doped ZnB₂O₄ (B = Al³⁺, Ga³⁺) Nanospinels: An Efficient Red Phosphor

This paper describes the synthesis of Eu­(III)-doped ZnB₂O₄ (B = Al­(III) or Ga­(III)) nanospinels with Eu­(III) concentrations varying between 1% and 15.6%. The synthesis was achieved through a microwave (MW) synthetic methodology producing 3 nm particles by the thermal decomposition of zinc undecylenate (UND) and a metal 2,4-pentanedionate (B­(acac)₃, B = Al³⁺ or Ga³⁺) in oleylamine (OAm). The nanospinels were then ligand exchanged with the β-diketonate, 2-thenoyltrifluoroacetone (tta). Using tta as a ligand on the surface of the particles resulted in soluble materials that could be embedded in lens mimics, such as poly­(methyl methacrylate) (PMMA). Through a Dexter energy transfer mechanism, tta efficiently sensitized the Eu­(III) doped within the nanospinels, resulting in red phosphors with intrinsic quantum efficiencies (QEs) and QEs in PMMA as high as 50% when excited in the UV. Optical measurements on the out of batch and tta-passivated nanospinels were done to obtain absorption, emission, and lifetime data. The structural properties of the nanospinels were evaluated by ICP-MS, pXRD, TEM, FT-IR, EXAFS, and XANES

Nature of the Positron State in CdSe Quantum Dots

Previous studies have shown that positron-annihilation spectroscopy is a highly sensitive probe of the electronic structure and surface composition of ligand-capped semiconductor quantum dots (QDs) embedded in thin films. The nature of the associated positron state, however, whether the positron is confined inside the QDs or localized at their surfaces, has so far remained unresolved. Our positron-annihilation lifetime spectroscopy studies of CdSe QDs reveal the presence of a strong lifetime component in the narrow range of 358-371 ps, indicating abundant trapping and annihilation of positrons at the surfaces of the QDs. Furthermore, our ab initio calculations of the positron wave function and lifetime employing a recent formulation of the weighted density approximation demonstrate the presence of a positron surface state and predict positron lifetimes close to experimental values. Our study thus resolves the long-standing question regarding the nature of the positron state in semiconductor QDs and opens the way to extract quantitative information on surface composition and ligand-surface interactions of colloidal semiconductor QDs through highly sensitive positron-annihilation techniques.RST/Fundamental Aspects of Materials and Energ

Actinide Arene-Metalates: Ion Pairing Effects on the Electronic Structure of Unsupported Uranium-Arene Sandwich Complexes

Chatt reaction methods were employed to synthesize the first well characterized actinide-arene sandwich complexes. Namely, addition of [UI2(THF)3(μ-OMe)]2⸱THF (2⸱THF) to THF solutions containing 6 equiv. of K[C14H10] generates the dimeric complexes [K(18-crown-6)(THF)2]2[U(η6-C14H10)(η4-C14H10)(μ-OMe)]2⸱4THF (118C6⸱4THF) and {[K(THF)3][U(η6-C14H10)(η4-C14H10)(μ-OMe)]}2 (1THF) upon crystallization of the products in THF in the presence or absence of 18-crown-6, respectively. Both 118C6⸱4THF and 1THF are thermally stable in the solid-state at room temperature; however, after crystallization, they become insoluble in THF or DME solutions and instead gradually decompose upon standing. X-ray diffraction analysis reveals 118C6⸱4THF and 1THF to be structurally similar, possessing uranium centers sandwiched between anthracene ligands of mixed tetrahapto and hexahapto ligation modes. Yet, the two complexes are distinguished by the close contact potassium-arene ion pairing that is seen in 1THF but absent in 118C6⸱4THF, which is observed to have a significant effect on the electronic characteristics of the two complexes. Structural analysis, SQUID magnetometry data, XANES spectral characterization, and computational analyses are generally consistent with U(IV) formal assignments for the metal centers in both 118C6⸱4THF and 1THF, though noticeable differences are detected between the two species. For instance, the effective magnetic moment of 1THF (3.74 µB) is significantly lower than that of 118C6⸱4THF (4.40 µB) at 300 K. Furthermore, the XANES data shows the U LIII-edge absorption energy for 1THF to be 0.9 eV higher than that of 118C6⸱4THF, suggestive of more oxidized metal centers in the former. Of note, CASSCF calculations on the model complex {[U(η6-C14H10)(η4-C14H10)(μ-OMe)]2}2- (1*) shows highly polarized uranium-arene interactions defined by π-type bonds where the metal contributions are primarily comprised by the 6d-orbitals (7.3± 0.6%) with minor participation from the 5f-orbitals (1.5 ± 0.5%). These unique complexes provide new insights into actinide-arene bonding interactions and show the sensitivity of the electronic structures of the uranium atoms to coordination sphere effects.<br /